CN103972586A - A non-aqueous organic electrolyte and preparation method thereof, and a lithium ion rechargeable battery - Google Patents

A non-aqueous organic electrolyte and preparation method thereof, and a lithium ion rechargeable battery Download PDF

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CN103972586A
CN103972586A CN201310031863.0A CN201310031863A CN103972586A CN 103972586 A CN103972586 A CN 103972586A CN 201310031863 A CN201310031863 A CN 201310031863A CN 103972586 A CN103972586 A CN 103972586A
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water organic
organic electrolyte
formula
lithium
electrolysis solution
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CN103972586B (en
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王圣
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Huawei Technologies Co Ltd
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
    • H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
    • H01M10/0566—Liquid materials
    • H01M10/0567—Liquid materials characterised by the additives
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M2300/00—Electrolytes
    • H01M2300/0017—Non-aqueous electrolytes
    • H01M2300/0025—Organic electrolyte
    • H01M2300/0028—Organic electrolyte characterised by the solvent
    • H01M2300/0037—Mixture of solvents
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/131—Electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Abstract

The embodiment of the invention provides a non-aqueous organic electrolytewhich includes: lithium salt, a non-aqueous organic solvent, and an additive in the non-aqueous organic electrolyte. The additive in the non-aqueous organic electrolyte is an additive in a non-aqueous organic electrolyte shown in formula (II), and/or an additive in a non-aqueous organic electrolyte shown in formula (II). The non-aqueous organic electrolytesolves the problem that when a battery system is at full charge high voltage, a non-aqueous organic electrolyte in the prior art with an active material of a positive pole is easy to carry out side reaction in the such battery system, which leads to decrease in cycle capacity of a lithium ion rechargeable battery, volume expansion and decline in discharge capacity. The non-aqueous organic electrolyte in the work environment about 4.9V high voltage still has excellent cycle performance. The embodiment of the invention also provides a preparation method of the non-aqueous organic electrolyte, and a lithium ion rechargeable battery containing the non-aqueous organic electrolyte.

Description

A kind of non-water organic electrolyte and preparation method thereof and lithium rechargeable battery
Technical field
The present invention relates to field of lithium ion secondary, particularly relate to a kind of non-water organic electrolyte and preparation method thereof and lithium rechargeable battery.
Background technology
Along with the expansion of lithium rechargeable battery application, comprise the introducing of the application scenarios that large-scale energy-accumulating power station, the standby electricity in high temperature base station etc. are new in recent years, people become more urgent to having the demand of high energy lithium ion secondary batteries.
In order to realize the high-energy of lithium rechargeable battery, generally realize by the operating voltage or the research and development high-energy positive electrode that improve lithium rechargeable battery.The high-voltage anode material of having reported has rich lithium solid solution xLi 2mnO 3(1-x) LiMO 2with spinelle LiNi 0.5mn 1.5o 4deng, its charging voltage is close to or higher than 5V, but the existing report of non-water organic electrolyte matching.The electrolyte of at present conventional lithium rechargeable battery is mainly 1M LiPF 6be dissolved in carbonates solvent, but it is in full charging high voltage (the above voltage of 4.5V) battery system, especially easily and positive electrode active materials generation side reaction and then oxidized decomposition, cause the decline of lithium rechargeable battery cycle performance, volumetric expansion and discharge capacity to decline, therefore cannot be applied to high-voltage lithium ion secondary cell system.
In recent years, there is part Study scholar to propose to add anti-oxidant current potential in non-water organic electrolyte and can arrive the high voltage solvents such as more than 5V sulfone class, nitrile, ionic liquid, in order to improve the non-oxidizability of non-water organic electrolyte, and then lithium rechargeable battery can be used under the voltage more than 4.5V.But the general viscosity of these high voltage solvents causes the conductivity of non-water organic electrolyte to reduce compared with senior general, and meanwhile, these high voltage wet with solvent are poor, therefore causes lithium rechargeable battery discharge capacity to decline.
Summary of the invention
For addressing the above problem, embodiment of the present invention first aspect aims to provide a kind of non-water organic electrolyte, the problem that easily causes the problem of the decline of lithium rechargeable battery cycle performance, volumetric expansion and discharge capacity decline in order to solve non-water organic electrolyte of the prior art in full charging high voltage (the above voltage of 4.5V) battery system with positive electrode active materials generation side reaction, this non-water organic electrolyte still shows good cycle performance in the high-tension operational environment in 4.9V left and right.Embodiment of the present invention second aspect aims to provide the preparation method of above-mentioned non-water organic electrolyte.The embodiment of the present invention third aspect aims to provide a kind of lithium rechargeable battery that comprises above-mentioned non-water organic electrolyte, and this lithium rechargeable battery has high-energy-density.
First aspect, the embodiment of the present invention provides a kind of non-water organic electrolyte, comprising:
Lithium salts;
Non-aqueous organic solvent; And
Non-water organic electrolysis solution additive, described non-water organic electrolysis solution additive is suc as formula the non-water organic electrolysis solution additive shown in (I) and/or suc as formula the non-water organic electrolysis solution additive shown in (II),
formula (I),
formula (II),
Wherein, R 1, R 2, R 3, R 4, R 5, R 6, R 7and R 8for C 1~ C 10straight or branched alkyl, C 1~ C 10alkylene, C 1~ C 10alkynes base or C 6~ C 14aromatic radical, or R 1, R 2, R 3, R 4, R 5, R 6, R 7and R 8for containing halogen: C 1~ C 10straight or branched alkyl, C 1~ C 10alkylene, C 1~ C 10alkynes base or C 6~ C 14aromatic radical.
Wherein, the derivative that the non-water organic electrolysis solution additive suc as formula shown in (I) in the embodiment of the present invention is pyrophosphate, the derivative that is pyrophosphite suc as formula the non-water organic electrolysis solution additive shown in (II).R 1, R 2, R 3and R 4can be identical structure, also can be different.R 5, R 6, R 7and R 8can be identical structure, also can be different.
Preferably, suc as formula R in the non-water organic electrolysis solution additive shown in (I) 1, R 2, R 3and R 4for methyl, ethyl, trifluoromethyl, trifluoroethyl, perfluor ethyl, phenyl, benzyl, part or perfluor substituted-phenyl.R 1, R 2, R 3and R 4can be identical structure, also can be different.
Preferably, suc as formula R in the non-water organic electrolysis solution additive shown in (II) 5, R 6, R 7and R 8for methyl, ethyl, trifluoromethyl, trifluoroethyl, perfluor ethyl, phenyl, benzyl, part or perfluor substituted-phenyl.R 5, R 6, R 7and R 8can be identical structure, also can be different.
Lithium salts, as carrier, in order to ensure the basic operation of lithium ion in lithium rechargeable battery, includes but not limited to lithium hexafluoro phosphate (LiPF 6), lithium perchlorate (LiClO 4), LiBF4 (LiBF 4), hexafluoroarsenate lithium (LiAsF 6), hexafluorosilicic acid lithium (LiSiF 6), tetraphenyl lithium borate (LiB (C 6h 5) 4), lithium chloride (LiCl), lithium bromide (LiBr), chlorine lithium aluminate (LiAlCl 4), di-oxalate lithium borate (LiBOB), trifluoromethyl sulfonic acid lithium (LiCF 3sO 3), perfluoro butyl Sulfonic Lithium (LiC 4f 9sO 3), fluoro sulfimide lithium (LiN (C xf 2x+1sO 2) (C yf 2y+1sO 2) (in formula, x and y are for being less than 21 natural numbers) and lithium iodide (LiI).
The final concentration of lithium salts in non-water organic electrolyte do not limit, and is generally 0.5 ~ 2.0mol/L.Preferably, the final concentration of lithium salts in non-water organic electrolyte is 0.7 ~ 1.6mol/L.Lithium salts final concentration is preferably within the scope of this time, and the non-water organic electrolyte of the embodiment of the present invention can provide better lithium ion conductivity and lithium ion mobility simultaneously.
Non-aqueous organic solvent is selected from the solvent of this area routine, can be the carbonic ester of fat or ring-type, ether, sulfone, nitrile, one or more in ionic liquid and their derivative, include but not limited to gamma-butyrolacton (GBL), vinyl carbonate (EC), diethyl carbonate (DEC), dimethyl carbonate (DMC), vinylene carbonate (VC), methyl ethyl carbonate (EMC), dipropyl carbonate (DPC), methyl propyl carbonate (MPC), propylene carbonate (PC), methyl formate (MF), methyl acrylate (MA), methyl butyrate (MB) ethyl acetate (EP), ethylene sulfite (ES), propylene sulfite (PS), methyl sulfide (DMS), diethyl sulfite (DES), oxolane, acid anhydrides, 1-METHYLPYRROLIDONE, N-METHYLFORMAMIDE, N-yl acetamide, acetonitrile, DMF, sulfolane, methyl-sulfoxide, dimethyl sulfite and other is fluorine-containing, sulfur-bearing or containing the ring-type organosilane ester of unsaturated bond.
Preferably, by mass fraction, non-aqueous organic solvent accounts for 85% ~ 99.5% of non-water organic electrolyte, and non-water organic electrolysis solution additive accounts for 0.5% ~ 15% of non-water organic electrolyte.
More preferably, by mass fraction, non-aqueous organic solvent accounts for 92% ~ 99% of non-water organic electrolyte, and non-water organic electrolysis solution additive accounts for 1% ~ 8% of non-water organic electrolyte.
In order to meet the application demand of non-water organic electrolyte under particular condition, preferably, non-water organic electrolyte also comprises function additive, and described function additive is selected from one or more in circulation additive, high temperature additive, flame-retardant additive and overcharging additive.Described function additive includes but not limited to vinylene carbonate (VC), biphenyl, cyclohexyl benzene, 2,52 di-tert-butyls 21,42 dimethoxy benzenes (DDB), thiophene, phenthazine, lithium carbonate, carbon dioxide, 1,3 propane sultone (PS), ethylene carbonate (FEC) and LiBF4 (LiBF4), trimethyl phosphate, triethyl phosphate, triphenyl phosphate, tributyl phosphate and phosphonitrile compounds.
Preferably, by mass fraction, function additive accounts for 0.1% ~ 15% of non-water organic electrolyte.
The non-water organic electrolyte of one that embodiment of the present invention first aspect provides can use in the operational environment of full charging high voltage (the above voltage of 4.5V), there is excellent chemical stability and electrochemical stability, the phenomenon that under high voltage, lithium rechargeable battery aerogenesis expands be can avoid, and cycle performance and the discharge capacity of lithium rechargeable battery under high voltage improved.This non-water organic electrolyte still shows good cycle performance in the high-tension operational environment in 4.9V left and right.This may be because: lithium rechargeable battery is in charging process, both positive and negative polarity potential difference constantly raises, when this potential difference reaches 4.5V and 4.5V when above, in non-water organic electrolyte suc as formula the non-water organic electrolysis solution additive shown in (I) and/or suc as formula the part phosphorus oxygen bond rupture of the non-water organic electrolysis solution additive shown in (II), product that the phosphorous fragment of part forms with non-aqueous organic solvent or the oxidized decomposition of lithium salts interacts and to form electronics at surface of positive electrode active material non-conductive, the skin covering of the surface that contains P elements of ionic conduction, cover the avtive spot of surface of positive electrode active material, on blocking-up surface of positive electrode active material, avtive spot contacts with the direct of non-water organic electrolyte, reduce the oxidation of positive electrode active materials to non-water organic electrolyte, thereby the cycle performance of lithium rechargeable battery under raising high voltage, and the situation of avoiding lithium rechargeable battery volumetric expansion and discharge capacity to decline.
Second aspect, the embodiment of the present invention provides a kind of preparation method of non-water organic electrolyte, comprises the following steps:
Lithium salts is dissolved in non-aqueous organic solvent, adds suc as formula the non-water organic electrolysis solution additive shown in (I) and/or suc as formula the non-water organic electrolysis solution additive shown in (II), stir, make non-water organic electrolyte,
formula (I),
formula (II),
Wherein, R 1, R 2, R 3, R 4, R 5, R 6, R 7and R 8for C 1~ C 10straight or branched alkyl, C 1~ C 10alkylene, C 1~ C 10alkynes base or C 6~ C 14aromatic radical, or R 1, R 2, R 3, R 4, R 5, R 6, R 7and R 8for containing halogen: C 1~ C 10straight or branched alkyl, C 1~ C 10alkylene, C 1~ C 10alkynes base or C 6~ C 14aromatic radical.
Preferably, suc as formula R in the non-water organic electrolysis solution additive shown in (I) 1, R 2, R 3and R 4for methyl, ethyl, trifluoromethyl, trifluoroethyl, perfluor ethyl, phenyl, benzyl, part or perfluor substituted-phenyl.R 1, R 2, R 3and R 4can be identical structure, also can be different.
Preferably, suc as formula R in the non-water organic electrolysis solution additive shown in (II) 5, R 6, R 7and R 8for methyl, ethyl, trifluoromethyl, trifluoroethyl, perfluor ethyl, phenyl, benzyl, part or perfluor substituted-phenyl.R 5, R 6, R 7and R 8can be identical structure, also can be different.
Preferably, the preparation method of described non-water organic electrolyte carries out in the glove box that is full of argon gas.
Preferably, lithium salts is dissolved in the process of non-aqueous organic solvent and stirs, controlling temperature is 20 ~ 35 DEG C.In this preferred range, can avoid non-aqueous organic solvent volatilization and avoid the decomposition of lithium salts, can avoid again that Yin Wendu is too low to be caused non-aqueous organic solvent to solidify and affect the situation that lithium salts dissolves and occur.
Lithium salts, as carrier, in order to ensure the basic operation of lithium ion in lithium rechargeable battery, includes but not limited to lithium hexafluoro phosphate (LiPF 6), lithium perchlorate (LiClO 4), LiBF4 (LiBF 4), hexafluoroarsenate lithium (LiAsF 6), hexafluorosilicic acid lithium (LiSiF 6), tetraphenyl lithium borate (LiB (C 6h 5) 4), lithium chloride (LiCl), lithium bromide (LiBr), chlorine lithium aluminate (LiAlCl 4), di-oxalate lithium borate (LiBOB), trifluoromethyl sulfonic acid lithium (LiCF 3sO 3), perfluoro butyl Sulfonic Lithium (LiC 4f 9sO 3), fluoro sulfimide lithium (LiN (C xf 2x+1sO 2) (C yf 2y+1sO 2) (in formula, x and y are for being less than 21 natural numbers) and lithium iodide (LiI).
The final concentration of lithium salts in non-water organic electrolyte do not limit, and is generally 0.5 ~ 2.0mol/L.Preferably, the final concentration of lithium salts in non-water organic electrolyte is 0.7 ~ 1.6mol/L.Lithium salts final concentration is preferably within the scope of this time, and the non-water organic electrolyte of the embodiment of the present invention can provide better lithium ion conductivity and lithium ion mobility simultaneously.
Non-aqueous organic solvent is selected from the solvent of this area routine, can be the carbonic ester of fat or ring-type, ether, sulfone, nitrile, one or more in ionic liquid and their derivative, include but not limited to gamma-butyrolacton (GBL), vinyl carbonate (EC), diethyl carbonate (DEC), dimethyl carbonate (DMC), vinylene carbonate (VC), methyl ethyl carbonate (EMC), dipropyl carbonate (DPC), methyl propyl carbonate (MPC), propylene carbonate (PC), methyl formate (MF), methyl acrylate (MA), methyl butyrate (MB) ethyl acetate (EP), ethylene sulfite (ES), propylene sulfite (PS), methyl sulfide (DMS), diethyl sulfite (DES), oxolane, acid anhydrides, 1-METHYLPYRROLIDONE, N-METHYLFORMAMIDE, N-yl acetamide, acetonitrile, DMF, sulfolane, methyl-sulfoxide, dimethyl sulfite and other is fluorine-containing, sulfur-bearing or containing the ring-type organosilane ester of unsaturated bond.
Preferably, by mass fraction, non-aqueous organic solvent accounts for 85% ~ 99.5% of non-water organic electrolyte, and non-water organic electrolysis solution additive accounts for 0.5% ~ 15% of non-water organic electrolyte.
More preferably, by mass fraction, non-aqueous organic solvent accounts for 92% ~ 99% of non-water organic electrolyte, and non-water organic electrolysis solution additive accounts for 1% ~ 8% of non-water organic electrolyte.
In order to meet the application demand of non-water organic electrolyte under particular condition, preferably, in the preparation method of a kind of non-water organic electrolyte that embodiment of the present invention second aspect provides, add suc as formula the non-water organic electrolysis solution additive shown in (I) and/or suc as formula after the non-water organic electrolysis solution additive shown in (II), also comprise and add function additive, described function additive is selected from circulation additive, high temperature additive, one or more in flame-retardant additive and overcharging additive, described function additive includes but not limited to vinylene carbonate (VC), biphenyl, cyclohexyl benzene, 2, 52 di-tert-butyls 21, 42 dimethoxy benzenes (DDB), thiophene, phenthazine, lithium carbonate, carbon dioxide, 1, 3 propane sultones, ethylene carbonate (FEC) and LiBF4 (LiBF 4), trimethyl phosphate, triethyl phosphate, triphenyl phosphate, tributyl phosphate and phosphonitrile compounds.
Preferably, by mass fraction, function additive accounts for 0.1% ~ 15% of non-water organic electrolyte.
The preparation method of a kind of non-water organic electrolyte that embodiment of the present invention second aspect provides provides a kind of new non-water organic electrolyte, and this preparation method's technique is simple.
The third aspect, the embodiment of the present invention provides a kind of lithium rechargeable battery, comprise: positive pole, negative pole, barrier film, housing and non-water organic electrolyte, described non-water organic electrolyte, comprise: lithium salts, non-aqueous organic solvent and suc as formula the non-water organic electrolysis solution additive shown in (I) and/or suc as formula the non-water organic electrolysis solution additive shown in (II)
formula (I),
formula (II),
Wherein, R 1, R 2, R 3, R 4, R 5, R 6, R 7and R 8for C 1~ C 10straight or branched alkyl, C 1~ C 10alkylene, C 1~ C 10alkynes base or C 6~ C 14aromatic radical, or R 1, R 2, R 3, R 4, R 5, R 6, R 7and R 8for containing halogen: C 1~ C 10straight or branched alkyl, C 1~ C 10alkylene, C 1~ C 10alkynes base or C 6~ C 14aromatic radical.
Described non-water organic electrolyte, as described in embodiment of the present invention first aspect, repeats no more herein.
Positive pole comprises the positive electrode active materials that can embed or deviate from lithium ion.Preferably, described positive electrode active materials has high removal lithium embedded platform under 4.5V and the above voltage of 4.5V in the time discharging and recharging removal lithium embedded ion.More preferably, described positive electrode active materials is LiM xmn (2-x)o 4, wherein M is selected from one or more in transition metal Ni, Co and Fe, 0≤x≤2.And more preferably, described positive electrode active materials is xLi 2mnO 3(1-x) LiMO 2, wherein M is selected from one or more in transition metal Ni, Co and Mn, 0≤x≤1.
The form of a kind of lithium rechargeable battery that the embodiment of the present invention third aspect provides is not limit, can be square, cylinder or soft-package battery, no matter be takeup type or stacked, this lithium rechargeable battery has high-energy-density, good cycle performance and discharge capacity.
The preparation method of this lithium rechargeable battery is: positive pole, negative pole and barrier film are made to Battery Pole Core, be placed in housing, inject described non-water organic electrolyte, sealing, obtains lithium rechargeable battery.Preparation method's simple and feasible of described lithium rechargeable battery.
The advantage of the embodiment of the present invention will partly be illustrated in the following description, and a part is apparent according to specification, or can know by the enforcement of the embodiment of the present invention.
Embodiment
The following stated is the preferred implementation of the embodiment of the present invention; should be understood that; for those skilled in the art; do not departing under the prerequisite of embodiment of the present invention principle; can also make some improvements and modifications, these improvements and modifications are also considered as the protection range of the embodiment of the present invention.
Embodiment of the present invention first aspect provides a kind of non-water organic electrolyte, the problem that easily causes the problem of the decline of lithium rechargeable battery cycle performance, volumetric expansion and discharge capacity decline in order to solve non-water organic electrolyte of the prior art in full charging high voltage (the above voltage of 4.5V) battery system with positive electrode active materials generation side reaction, this non-water organic electrolyte still shows good cycle performance in the high-tension operational environment in 4.9V left and right.Embodiment of the present invention second aspect provides the preparation method of above-mentioned non-water organic electrolyte.The embodiment of the present invention third aspect provides a kind of lithium rechargeable battery that comprises above-mentioned non-water organic electrolyte, and this lithium rechargeable battery has high-energy-density.
First aspect, the embodiment of the present invention provides a kind of non-water organic electrolyte, comprising:
Lithium salts;
Non-aqueous organic solvent; And
Non-water organic electrolysis solution additive, described non-water organic electrolysis solution additive is suc as formula the non-water organic electrolysis solution additive shown in (I) and/or suc as formula the non-water organic electrolysis solution additive shown in (II),
formula (I),
formula (II),
Wherein, R 1, R 2, R 3, R 4, R 5, R 6, R 7and R 8for C 1~ C 10straight or branched alkyl, C 1~ C 10alkylene, C 1~ C 10alkynes base or C 6~ C 14aromatic radical, or R 1, R 2, R 3, R 4, R 5, R 6, R 7and R 8for containing halogen: C 1~ C 10straight or branched alkyl, C 1~ C 10alkylene, C 1~ C 10alkynes base or C 6~ C 14aromatic radical.
Wherein, the derivative that the non-water organic electrolysis solution additive suc as formula shown in (I) in the embodiment of the present invention is pyrophosphate, the derivative that is pyrophosphite suc as formula the non-water organic electrolysis solution additive shown in (II).R 1, R 2, R 3and R 4can be identical structure, also can be different.R 5, R 6, R 7and R 8can be identical structure, also can be different.
Suc as formula R in the non-water organic electrolysis solution additive shown in (I) 1, R 2, R 3and R 4for methyl, ethyl, trifluoromethyl, trifluoroethyl, perfluor ethyl, phenyl, benzyl, part or perfluor substituted-phenyl.R 1, R 2, R 3and R 4can be identical structure, also can be different.
Suc as formula R in the non-water organic electrolysis solution additive shown in (II) 5, R 6, R 7and R 8for methyl, ethyl, trifluoromethyl, trifluoroethyl, perfluor ethyl, phenyl, benzyl, part or perfluor substituted-phenyl.R 5, R 6, R 7and R 8can be identical structure, also can be different.
Lithium salts, as carrier, in order to ensure the basic operation of lithium ion in lithium rechargeable battery, includes but not limited to lithium hexafluoro phosphate (LiPF 6), lithium perchlorate (LiClO 4), LiBF4 (LiBF 4), hexafluoroarsenate lithium (LiAsF 6), hexafluorosilicic acid lithium (LiSiF 6), tetraphenyl lithium borate (LiB (C 6h 5) 4), lithium chloride (LiCl), lithium bromide (LiBr), chlorine lithium aluminate (LiAlCl 4), di-oxalate lithium borate (LiBOB), trifluoromethyl sulfonic acid lithium (LiCF 3sO 3), perfluoro butyl Sulfonic Lithium (LiC 4f 9sO 3), fluoro sulfimide lithium (LiN (C xf 2x+1sO 2) (C yf 2y+1sO 2) (in formula, x and y are for being less than 21 natural numbers) and lithium iodide (LiI).
The final concentration of lithium salts in non-water organic electrolyte do not limit, and is generally 0.5 ~ 2.0mol/L.Be specifically as follows, the final concentration of lithium salts in non-water organic electrolyte is 0.7～1.6mol/L.Lithium salts final concentration is preferably within the scope of this time, and the non-water organic electrolyte of the embodiment of the present invention can provide better lithium ion conductivity and lithium ion mobility simultaneously.
Non-aqueous organic solvent is selected from the solvent of this area routine, can be the carbonic ester of fat or ring-type, ether, sulfone, nitrile, one or more in ionic liquid and their derivative, include but not limited to gamma-butyrolacton (GBL), vinyl carbonate (EC), diethyl carbonate (DEC), dimethyl carbonate (DMC), vinylene carbonate (VC), methyl ethyl carbonate (EMC), dipropyl carbonate (DPC), methyl propyl carbonate (MPC), propylene carbonate (PC), methyl formate (MF), methyl acrylate (MA), methyl butyrate (MB) ethyl acetate (EP), ethylene sulfite (ES), propylene sulfite (PS), methyl sulfide (DMS), diethyl sulfite (DES), oxolane, acid anhydrides, 1-METHYLPYRROLIDONE, N-METHYLFORMAMIDE, N-yl acetamide, acetonitrile, DMF, sulfolane, methyl-sulfoxide, dimethyl sulfite and other is fluorine-containing, sulfur-bearing or containing the ring-type organosilane ester of unsaturated bond.
By mass fraction, non-aqueous organic solvent accounts for 85% ~ 99.5% of non-water organic electrolyte, and non-water organic electrolysis solution additive accounts for 0.5% ~ 15% of non-water organic electrolyte.Particularly, by mass fraction, non-aqueous organic solvent accounts for 92% ~ 99% of non-water organic electrolyte, and non-water organic electrolysis solution additive accounts for 1% ~ 8% of non-water organic electrolyte.
In order to meet the application demand of non-water organic electrolyte under particular condition, non-water organic electrolyte can also comprise function additive, and described function additive is selected from one or more in circulation additive, high temperature additive, flame-retardant additive and overcharging additive.Described function additive includes but not limited to vinylene carbonate (VC), biphenyl, cyclohexyl benzene, 2,52 di-tert-butyls 21,42 dimethoxy benzenes (DDB), thiophene, phenthazine, lithium carbonate, carbon dioxide, 1,3 propane sultone (PS), ethylene carbonate (FEC) and LiBF4 (LiBF 4), trimethyl phosphate, triethyl phosphate, triphenyl phosphate, tributyl phosphate and phosphonitrile compounds.
By mass fraction, function additive accounts for 0.1% ~ 15% of non-water organic electrolyte.
The non-water organic electrolyte of one that embodiment of the present invention first aspect provides can use in the operational environment of full charging high voltage (the above voltage of 4.5V), there is excellent chemical stability and electrochemical stability, the phenomenon that under high voltage, lithium rechargeable battery aerogenesis expands be can avoid, and cycle performance and the discharge capacity of lithium rechargeable battery under high voltage improved.This non-water organic electrolyte still shows good cycle performance in the high-tension operational environment in 4.9V left and right.This may be because: lithium rechargeable battery is in charging process, both positive and negative polarity potential difference constantly raises, when this potential difference reaches 4.5V and 4.5V when above, in non-water organic electrolyte suc as formula the non-water organic electrolysis solution additive shown in (I) and/or suc as formula the part phosphorus oxygen bond rupture of the non-water organic electrolysis solution additive shown in (II), product that the phosphorous fragment of part forms with non-aqueous organic solvent or the oxidized decomposition of lithium salts interacts and to form electronics at surface of positive electrode active material non-conductive, the skin covering of the surface that contains P elements of ionic conduction, cover the avtive spot of surface of positive electrode active material, on blocking-up surface of positive electrode active material, avtive spot contacts with the direct of non-water organic electrolyte, reduce the oxidation of positive electrode active materials to non-water organic electrolyte, thereby the cycle performance of lithium rechargeable battery under raising high voltage, and the situation of avoiding lithium rechargeable battery volumetric expansion and discharge capacity to decline.
Second aspect, the embodiment of the present invention provides a kind of preparation method of non-water organic electrolyte, comprises the following steps:
Lithium salts is dissolved in non-aqueous organic solvent, adds suc as formula the non-water organic electrolysis solution additive shown in (I) and/or suc as formula the non-water organic electrolysis solution additive shown in (II), stir, make non-water organic electrolyte,
formula (I),
formula (II),
Wherein, R 1, R 2, R 3, R 4, R 5, R 6, R 7and R 8for C 1~ C 10straight or branched alkyl, C 1~ C 10alkylene, C 1~ C 10alkynes base or C 6~ C 14aromatic radical, or R 1, R 2, R3, R 2, R 5, R 6, R 7and R 8for containing halogen: C 1~ C 10straight or branched alkyl, C 1~ C 10alkylene, C 1~ C 10alkynes base or C 6~ C 14aromatic radical.
Suc as formula R in the non-water organic electrolysis solution additive shown in (I) 1, R 2, R 3and R 4for methyl, ethyl, trifluoromethyl, trifluoroethyl, perfluor ethyl, phenyl, benzyl, part or perfluor substituted-phenyl.R 1, R 2, R 3and R 4can be identical structure, also can be different.
Suc as formula R in the non-water organic electrolysis solution additive shown in (II) 5, R 6, R 7and R 8for methyl, ethyl, trifluoromethyl, trifluoroethyl, perfluor ethyl, phenyl, benzyl, part or perfluor substituted-phenyl.R 5, R 6, R 7and R 8can be identical structure, also can be different.
The preparation method of described non-water organic electrolyte carries out in the glove box that is full of argon gas.
Lithium salts is dissolved in the process of non-aqueous organic solvent and stirs, controlling temperature is 20 ~ 35 DEG C.In this preferred range, can avoid non-aqueous organic solvent volatilization and avoid the decomposition of lithium salts, can avoid again that Yin Wendu is too low to be caused non-aqueous organic solvent to solidify and affect the situation that lithium salts dissolves and occur.
Lithium salts, as carrier, in order to ensure the basic operation of lithium ion in lithium rechargeable battery, includes but not limited to lithium hexafluoro phosphate (LiPF 6), lithium perchlorate (LiClO 4), LiBF4 (LiBF 4), hexafluoroarsenate lithium (LiAsF 6), hexafluorosilicic acid lithium (LiSiF 6), tetraphenyl lithium borate (LiB (C 6h 5) 4), lithium chloride (LiCl), lithium bromide (LiBr), chlorine lithium aluminate (LiAlCl 4), di-oxalate lithium borate (LiBOB), trifluoromethyl sulfonic acid lithium (LiCF 3sO 3), perfluoro butyl Sulfonic Lithium (LiC 4f 9sO 3), fluoro sulfimide lithium (LiN (C xf 2x+1sO 2) (C yf 2y+1sO 2) (in formula, x and y are for being less than 21 natural numbers) and lithium iodide (LiI).
The final concentration of lithium salts in non-water organic electrolyte do not limit, and is generally 0.5 ~ 2.0mol/L.Be specifically as follows, the final concentration of lithium salts in non-water organic electrolyte is 0.7～1.6mol/L.Lithium salts final concentration is preferably within the scope of this time, and the non-water organic electrolyte of the embodiment of the present invention can provide better lithium ion conductivity and lithium ion mobility simultaneously.
Non-aqueous organic solvent is selected from the solvent of this area routine, can be the carbonic ester of fat or ring-type, ether, sulfone, nitrile, one or more in ionic liquid and their derivative, include but not limited to gamma-butyrolacton (GBL), vinyl carbonate (EC), diethyl carbonate (DEC), dimethyl carbonate (DMC), vinylene carbonate (VC), methyl ethyl carbonate (EMC), dipropyl carbonate (DPC), methyl propyl carbonate (MPC), propylene carbonate (PC), methyl formate (MF), methyl acrylate (MA), methyl butyrate (MB) ethyl acetate (EP), ethylene sulfite (ES), propylene sulfite (PS), methyl sulfide (DMS), diethyl sulfite (DES), oxolane, acid anhydrides, 1-METHYLPYRROLIDONE, N-METHYLFORMAMIDE, N-yl acetamide, acetonitrile, DMF, sulfolane, methyl-sulfoxide, dimethyl sulfite and other is fluorine-containing, sulfur-bearing or containing the ring-type organosilane ester of unsaturated bond.
By mass fraction, non-aqueous organic solvent accounts for 85% ~ 99.5% of non-water organic electrolyte, and non-water organic electrolysis solution additive accounts for 0.5% ~ 15% of non-water organic electrolyte.Particularly, by mass fraction, non-aqueous organic solvent accounts for 92% ~ 99% of non-water organic electrolyte, and non-water organic electrolysis solution additive accounts for 1% ~ 8% of non-water organic electrolyte.
In order to meet the application demand of non-water organic electrolyte under particular condition, in the preparation method of a kind of non-water organic electrolyte that embodiment of the present invention second aspect provides, add suc as formula the non-water organic electrolysis solution additive shown in (I) and/or suc as formula after the non-water organic electrolysis solution additive shown in (II), also comprise and add function additive, described function additive is selected from circulation additive, high temperature additive, one or more in flame-retardant additive and overcharging additive, described function additive includes but not limited to vinylene carbonate (VC), biphenyl, cyclohexyl benzene, 2, 52 di-tert-butyls 21, 42 dimethoxy benzenes (DDB), thiophene, phenthazine, lithium carbonate, carbon dioxide, 1, 3 propane sultones, ethylene carbonate (FEC) and LiBF4 (LiBF 4), trimethyl phosphate, triethyl phosphate, triphenyl phosphate, tributyl phosphate and phosphonitrile compounds.
By mass fraction, function additive accounts for 0.1% ~ 15% of non-water organic electrolyte.
The preparation method of a kind of non-water organic electrolyte that embodiment of the present invention second aspect provides provides a kind of new non-water organic electrolyte, and this preparation method's technique is simple.
The third aspect, the embodiment of the present invention provides a kind of lithium rechargeable battery, comprise: positive pole, negative pole, barrier film, housing and non-water organic electrolyte, described non-water organic electrolyte, comprise: lithium salts, non-aqueous organic solvent and suc as formula the non-water organic electrolysis solution additive shown in (I) and/or suc as formula the non-water organic electrolysis solution additive shown in (II)
formula (I),
formula (II),
Wherein, R 1, R 2, R 3, R 4, R 5, R 6, R 7and R 8for C 1~ C 10straight or branched alkyl, C 1~ C 10alkylene, C 1~ C 10alkynes base or C 6~ C 14aromatic radical, or R 1, R 2, R 3, R 4, R 5, R 6, R 7and R 8for containing halogen: C 1~ C 10straight or branched alkyl, C 1~ C 10alkylene, C 1~ C 10alkynes base or C 6~ C 14aromatic radical.
Described non-water organic electrolyte, as described in embodiment of the present invention first aspect, repeats no more herein.
Positive pole comprises the positive electrode active materials that can embed or deviate from lithium ion.Described positive electrode active materials has high removal lithium embedded platform under 4.5V and the above voltage of 4.5V in the time discharging and recharging removal lithium embedded ion.Described positive electrode active materials can be LiM xmn (2-x)o 4, wherein M is selected from one or more in transition metal Ni, Co and Fe, 0≤x≤2.And described positive electrode active materials can be xLi 2mnO 3(1-x) LiMO 2, wherein M is selected from one or more in transition metal Ni, Co and Mn, 0≤x≤1.
The form of a kind of lithium rechargeable battery that the embodiment of the present invention third aspect provides is not limit, can be square, cylinder or soft-package battery, no matter be takeup type or stacked, this lithium rechargeable battery has high-energy-density, good cycle performance and discharge capacity.
The preparation method of this lithium rechargeable battery is: positive pole, negative pole and barrier film are made to Battery Pole Core, be placed in housing, inject described non-water organic electrolyte, sealing, obtains lithium rechargeable battery.Preparation method's simple and feasible of described lithium rechargeable battery.
Embodiment mono-
A preparation method for non-water organic electrolyte, comprises the following steps:
In blender, add 500 grams of ethylene carbonates (EC) and 500 grams of methyl ethyl carbonates (EMC) mixing to be made into non-aqueous organic solvent, by 125 grams of lithium salts LiPF 6be dissolved in non-aqueous organic solvent, stir, whipping temp is 28 DEG C;
Adding the purity of buying from Beijing Chemsun Pharmaceutical Technology Co., Ltd. is 99.5% suc as formula 5.65 grams of non-water organic electrolysis solution additive pyrophosphoric acid four (trifluoromethyl) esters shown in I a, stir, make non-water organic electrolyte A, by mass fraction, non-water organic electrolysis solution additive I a accounts for 0.5% of non-water organic electrolyte.
Taking the example that is made as of square coiled lithium ion secondary soft-package battery (model is as 423450-800mAh), the preparation method of embodiment of the present invention lithium rechargeable battery is described below.
The preparation of positive plate
By positive electrode active materials LiNi 0.5mn 1.5o 4, conductive agent acetylene black and binding agent PVDF dusty material mix according to mass ratio 80:10:10, then add 1-METHYLPYRROLIDONE (NMP) solution, in de-airing mixer, stir 2h, being prepared into oil is slurry, finally slurry is coated in to aluminium collector two sides, through 110 DEG C of oven dry, rolling, makes lithium-ion secondary battery positive plate.
The preparation of negative plate
Negative active core-shell material Delanium powder, binding agent carboxymethyl cellulose (CMC), binding agent styrene butadiene ribber (SBR) emulsion are mixed according to mass ratio 100:3:2, then add deionized water to be prepared into water system cathode size, finally slurry is coated in to copper current collector two sides, make lithium ion secondary battery negative pole sheet, negative plate Capacity design is 1.2 times of positive plate capacity.
The non-water organic electrolyte A that non-water organic electrolyte adopts the present embodiment to make.
The making of lithium rechargeable battery
The composite diaphragm of polypropylene and polyethylene composition is put between the anode pole piece and cathode pole piece of above-mentioned preparation, as sandwich structure, then roll into together 423450 square battery pole pieces, finally complete square coiling soft-package battery, finally inject non-water organic electrolyte A, obtain lithium rechargeable battery A.
For lithium rechargeable battery, no matter be square or cylinder or soft-package battery, no matter be also takeup type or stacked, adopt above-mentioned lithium rechargeable battery preparation method can obtain identical effect.
Embodiment bis-
A preparation method for non-water organic electrolyte, comprises the following steps:
In blender, add 500 grams of ethylene carbonates (EC), 1000 grams of dimethyl carbonates (DMC) and 500 grams of diethyl carbonates (DEC) mixing to be made into non-aqueous organic solvent, 250 grams of lithium salts LiClO4 are dissolved in non-aqueous organic solvent, stir, whipping temp is 20 DEG C;
Adding the purity of buying from Beijing Chemsun Pharmaceutical Technology Co., Ltd. is 99.5% suc as formula 22.73 grams of the non-water organic electrolysis solution additive pyrophosphoric acid four benzyl esters shown in I b, stir, make non-water organic electrolyte B, by mass fraction, non-water organic electrolysis solution additive I b accounts for 1% of non-water organic electrolyte.
Taking the example that is made as of square coiled lithium ion secondary soft-package battery (model is as 423450-800mAh), the preparation method of embodiment of the present invention lithium rechargeable battery is described below.
The preparation of positive plate
By positive electrode active materials LiNi 0.5mn 1.5o 4, conductive agent hydrocarbon black powder and binding agent PVDF dusty material mix according to mass ratio 85:10:5, then add 1-METHYLPYRROLIDONE (NMP) solution, in de-airing mixer, stir 2h, being prepared into oil is slurry, finally slurry is coated in to aluminium collector two sides, through 110 DEG C of oven dry, rolling, makes lithium-ion secondary battery positive plate.
The non-water organic electrolyte B that non-water organic electrolyte adopts the present embodiment to make, other,, by the manufacture method of the lithium rechargeable battery with embodiment mono-, makes lithium rechargeable battery B.
Embodiment tri-
A preparation method for non-water organic electrolyte, comprises the following steps:
In blender, add 500 grams of ethylene carbonates (EC) and 500 grams of diethyl carbonates (DEC) mixing to be made into non-aqueous organic solvent, by 200 grams of lithium salts tetraphenyl lithium borate LiB (C 6h 5) 4in non-aqueous organic solvent, stir, whipping temp is 25 DEG C;
Adding the purity of buying from Beijing Si Wangdakang scientific & trading Co., Ltd. is 99.5% suc as formula 104.35 grams of the non-water organic electrolysis solution additive tetraethyl pyrophosphates shown in I c, stir, make non-water organic electrolyte C, by mass fraction, non-water organic electrolysis solution additive I c accounts for 8% of non-water organic electrolyte.
Taking the example that is made as of square coiled lithium ion secondary soft-package battery (model is as 423450-800mAh), the preparation method of embodiment of the present invention lithium rechargeable battery is described below.
The preparation of positive plate
By positive electrode active materials 0.5 (Li 2mnO 3) 0.5 (LiNi 1/3co 1/3mn 1/3o 2), conductive agent hydrocarbon black powder and binding agent PVDF dusty material mix according to mass ratio 85:10:5, then add 1-METHYLPYRROLIDONE (NMP) solution, in de-airing mixer, stir 2h, being prepared into oil is slurry, finally slurry is coated in to aluminium collector two sides, through 110 DEG C of oven dry, rolling, makes lithium-ion secondary battery positive plate.
The non-water organic electrolyte C that non-water organic electrolyte adopts the present embodiment to make, other,, by the manufacture method of the lithium rechargeable battery with embodiment mono-, makes lithium rechargeable battery C.
Embodiment tetra-
A preparation method for non-water organic electrolyte, comprises the following steps:
In blender, add 500 grams of ethylene carbonates (EC) and 500 grams of dimethyl carbonates (DMC) mixing to be made into non-aqueous organic solvent, by 100 grams of lithium salts trimethyl fluoride sulfonyl lithium (LiCF 3sO 3) in non-aqueous organic solvent, stir, whipping temp is 25 DEG C;
Adding the purity of buying from Beijing Chemsun Pharmaceutical Technology Co., Ltd. is 99.5% suc as formula 194 grams of the non-water organic electrolysis solution additive pyrophosphoric acid four benzyl esters shown in I b, stir, make non-water organic electrolyte D, by mass fraction, non-water organic electrolysis solution additive I b accounts for 15% of non-water organic electrolyte.
Taking the example that is made as of square coiled lithium ion secondary soft-package battery (model is as 423450-800mAh), the preparation method of embodiment of the present invention lithium rechargeable battery is described below.
The preparation of positive plate
By positive electrode active materials 0.7 (Li 2mnO 3) 0.3 (LiNi 1/3co 1/3mn 1/3o 2), conductive agent hydrocarbon black powder and binding agent PVDF dusty material mix according to mass ratio 85:10:5, then add 1-METHYLPYRROLIDONE (NMP) solution, in de-airing mixer, stir 2h, being prepared into oil is slurry, finally slurry is coated in to aluminium collector two sides, through 110 DEG C of oven dry, rolling, makes lithium-ion secondary battery positive plate.
The non-water organic electrolyte D that non-water organic electrolyte adopts the present embodiment to make, other,, by the manufacture method of the lithium rechargeable battery with embodiment mono-, makes lithium rechargeable battery D.
Embodiment five
A preparation method for non-water organic electrolyte, comprises the following steps:
In blender, add 500 grams of ethylene carbonates (EC), 1000 grams of dimethyl carbonates (DMC) and 500 grams of methyl ethyl carbonates (EMC) mixing to be made into non-aqueous organic solvent, by 250 grams of lithium salts LiPF 6in non-aqueous organic solvent, stir, whipping temp is 25 DEG C;
Adding the purity of buying from Beijing Chemsun Pharmaceutical Technology Co., Ltd. is 99.5% suc as formula non-water organic electrolysis solution additive pyrophosphoric acid 22.73 grams and the 2.27 grams vinylene carbonates of four benzyl esters (VC) shown in I b, stir, make non-water organic electrolyte E, by mass fraction, non-water organic electrolysis solution additive I b accounts for 1% of non-water organic electrolyte, and function additive vinylene carbonate (VC) accounts for 0.1% of non-water organic electrolyte.
Taking the example that is made as of square coiled lithium ion secondary soft-package battery (model is as 423450-800mAh), the preparation method of embodiment of the present invention lithium rechargeable battery is described below.
The preparation of positive plate
By positive electrode active materials LiNi 0.5mn 1.5o 4, conductive agent hydrocarbon black powder and binding agent PVDF dusty material mix according to mass ratio 85:10:5, then add 1-METHYLPYRROLIDONE (NMP) solution, in de-airing mixer, stir 2h, being prepared into oil is slurry, finally slurry is coated in to aluminium collector two sides, through 110 DEG C of oven dry, rolling, makes lithium-ion secondary battery positive plate.
The non-water organic electrolyte E that non-water organic electrolyte adopts the present embodiment to make, other,, by the manufacture method of the lithium rechargeable battery with embodiment mono-, makes lithium rechargeable battery E.
Embodiment six
A preparation method for non-water organic electrolyte, comprises the following steps:
In blender, add 500 grams of ethylene carbonates (EC) and 500 grams of diethyl carbonates (DEC) mixing to be made into non-aqueous organic solvent, by 125 grams of lithium salts LiPF 6in non-aqueous organic solvent, stir, whipping temp is 25 DEG C;
Adding the purity of buying from Beijing Si Wangdakang scientific & trading Co., Ltd. is 99.5% suc as formula 11.36 grams of the non-water organic electrolysis solution additive pyrophosphorous acid tetra-ethyl esters shown in II a, stir, make non-water organic electrolyte F, by mass fraction, non-water organic electrolysis solution additive II a accounts for 1% of non-water organic electrolyte.
Taking the example that is made as of square coiled lithium ion secondary soft-package battery (model is as 423450-800mAh), the preparation method of embodiment of the present invention lithium rechargeable battery is described below.
The preparation of positive plate
By positive electrode active materials LiNi 0.5mn 1.5o 4, conductive agent hydrocarbon black powder and binding agent PVDF dusty material mix according to mass ratio 85:10:5, then add 1-METHYLPYRROLIDONE (NMP) solution, in de-airing mixer, stir 2h, being prepared into oil is slurry, finally slurry is coated in to aluminium collector two sides, through 110 DEG C of oven dry, rolling, makes lithium-ion secondary battery positive plate.
The non-water organic electrolyte F that non-water organic electrolyte adopts the present embodiment to make, other,, by the manufacture method of the lithium rechargeable battery with embodiment mono-, makes lithium rechargeable battery F.
Embodiment seven
A preparation method for non-water organic electrolyte, comprises the following steps:
In blender, add 500 grams of ethylene carbonates (EC), 1000 grams of dimethyl carbonates (DMC) and 500 grams of diethyl carbonates (DEC) mixing to be made into non-aqueous organic solvent, by 250 grams of lithium salts LiB (C 6h 5) 4in non-aqueous organic solvent, stir, whipping temp is 25 DEG C;
Adding the purity of buying from Beijing Si Wangdakang scientific & trading Co., Ltd. is 99.5% suc as formula 195.65 grams of the non-water organic electrolysis solution additive pyrophosphorous acid four benzyl esters shown in II b, stir, make non-water organic electrolyte G, by mass fraction, non-water organic electrolysis solution additive II b accounts for 8% of non-water organic electrolyte.
Taking the example that is made as of square coiled lithium ion secondary soft-package battery (model is as 423450-800mAh), the preparation method of embodiment of the present invention lithium rechargeable battery is described below.
The preparation of positive plate
By positive electrode active materials 0.4 (Li 2mnO 3) 0.6 (LiNi 1/3co 1/3mn 1/3o 2), conductive agent hydrocarbon black powder and binding agent PVDF dusty material mix according to mass ratio 85:10:5, then add 1-METHYLPYRROLIDONE (NMP) solution, in de-airing mixer, stir 2h, being prepared into oil is slurry, finally slurry is coated in to aluminium collector two sides, through 110 DEG C of oven dry, rolling, makes lithium-ion secondary battery positive plate.
The non-water organic electrolyte G that non-water organic electrolyte adopts the present embodiment to make, other,, by the manufacture method of the lithium rechargeable battery with embodiment mono-, makes lithium rechargeable battery G.
Embodiment eight
A preparation method for non-water organic electrolyte, comprises the following steps:
In blender, add 500 grams of ethylene carbonates (EC) and 500 grams of dimethyl carbonates (DMC) mixing to be made into non-aqueous organic solvent, by 125 grams of lithium salts LiCF 3sO 3in non-aqueous organic solvent, stir, whipping temp is 25 DEG C;
Adding the purity of buying from Beijing Si Wangdakang scientific & trading Co., Ltd. is 99.5% suc as formula non-water organic electrolysis solution additive pyrophosphorous acid 27.09 grams and the 202.58 grams triethyl phosphates of four benzyl esters (TEP) shown in II b, stir, make non-water organic electrolyte H, by mass fraction, non-water organic electrolysis solution additive II b accounts for 2% of non-water organic electrolyte, and function additive triethyl phosphate (TEP) accounts for 15% of non-water organic electrolyte.
Taking the example that is made as of square coiled lithium ion secondary soft-package battery (model is as 423450-800mAh), the preparation method of embodiment of the present invention lithium rechargeable battery is described below.
The preparation of positive plate
By positive electrode active materials LiNi 0.5mn 1.5o 4, conductive agent hydrocarbon black powder and binding agent PVDF dusty material mix according to mass ratio 85:10:5, then add 1-METHYLPYRROLIDONE (NMP) solution, in de-airing mixer, stir 2h, being prepared into oil is slurry, finally slurry is coated in to aluminium collector two sides, through 110 DEG C of oven dry, rolling, makes lithium-ion secondary battery positive plate.
The non-water organic electrolyte H that non-water organic electrolyte adopts the present embodiment to make, other,, by the manufacture method of the lithium rechargeable battery with embodiment mono-, makes lithium rechargeable battery H.
Comparative example one
In blender, add 500 grams of ethylene carbonates (EC) and 500 grams of methyl ethyl carbonates (EMC) mixing to be made into non-aqueous organic solvent, by 125 grams of lithium salts LiPF 6be dissolved in non-aqueous organic solvent, stir, make non-water organic electrolyte I.
Taking the example that is made as of square coiled lithium ion secondary soft-package battery (model is as 423450-800mAh), the preparation method of comparative example lithium rechargeable battery of the present invention is described below.
The preparation of positive plate
By positive electrode active materials LiNi 0.5mn 1.5o 4, conductive agent hydrocarbon black powder and binding agent PVDF dusty material mix according to mass ratio 85:10:5, then add 1-METHYLPYRROLIDONE (NMP) solution, in de-airing mixer, stir 2h, being prepared into oil is slurry, finally slurry is coated in to aluminium collector two sides, through 110 DEG C of oven dry, rolling, makes lithium-ion secondary battery positive plate.
The non-water organic electrolyte I that non-water organic electrolyte adopts this comparative example to make, other,, by the manufacture method of the lithium rechargeable battery with embodiment mono-, makes lithium rechargeable battery I.
Comparative example two
In blender, add 500 grams of ethylene carbonates (EC) and 500 grams of diethyl carbonates (DEC) mixing to be made into non-aqueous organic solvent, by 125 grams of lithium salts LiPF 6be dissolved in non-aqueous organic solvent, add 198.53 grams of function additive triethyl phosphates (TEP), stir, make non-water organic electrolyte J, by mass fraction, function additive triethyl phosphate (TEP) accounts for 15% of non-water organic electrolyte.
Taking the example that is made as of square coiled lithium ion secondary soft-package battery (model is as 423450-800mAh), the preparation method of comparative example lithium rechargeable battery of the present invention is described below.
The preparation of positive plate
By positive electrode active materials 0.5 (Li 2mnO 3) 0.5 (LiNi 1/3co 1/3mn 1/3o 2), conductive agent hydrocarbon black powder and binding agent PVDF dusty material mix according to mass ratio 85:10:5, then add 1-METHYLPYRROLIDONE (NMP) solution, in de-airing mixer, stir 2h, being prepared into oil is slurry, finally slurry is coated in to aluminium collector two sides, through 110 DEG C of oven dry, rolling, makes lithium-ion secondary battery positive plate.
The non-water organic electrolyte J that non-water organic electrolyte adopts this comparative example to make, other,, by the manufacture method of the lithium rechargeable battery with embodiment mono-, makes lithium rechargeable battery J.
Effect embodiment
1. the test of non-water organic electrolyte decomposition electric potential
Adopt three-electrode system to carry out cyclic voltammetry to embodiment mono-to eight, comparative example one, two, work electrode is vitreous carbon, is lithium electrode to electrode and reference electrode, and sweep limits is 0～5.5V, and sweep speed is 10mV/S.
Test result is in table 1.
The decomposition electric potential test of table 1. embodiment mono-~ eight and the non-water organic electrolyte of comparative example one ~ bis-
From the results shown in Table 1, the non-water organic electrolyte that the embodiment of the present invention one to eight provides, oxidation Decomposition current potential is all more than or equal to 5.0V, the non-water organic electrolyte oxidation Decomposition current potential that does not add pyrophosphate or pyrophosphite class additive in comparative example one and two only has 4.4V, far below the decomposition electric potential of the non-water organic electrolyte providing in the embodiment of the present invention one to eight.
2. lithium rechargeable battery cycle performance test
To carry out cycle performance test according to above-described embodiment one to eight and comparative example one and two prepared lithium rechargeable batteries.Method of testing is: pack lithium rechargeable battery into secondary cell performance test with correct method upper with BS-9300, first with 1C constant-current constant-voltage charging to 4.9V(for spinelle LiM xmn (2-x)o 4, wherein M is selected from one or more in transition metal Ni, Co and Fe, 0≤x≤2) or 4.6V(for rich lithium solid solution cathode material xLi 2mnO 3(1-x) LiMO 2, wherein M is selected from one or more in transition metal Ni, Co and Mn, 0≤x≤1), shelve 5 minutes, be discharged to 3.0V with 1C, then with 1C constant-current constant-voltage charging to 4.9V(for spinelle LiM xmn (2-x)o 4, wherein M is selected from one or more in transition metal Ni, Co and Fe, 0≤x≤2) or 4.6V(for rich lithium solid solution cathode material xLi 2mnO 3(1-x) LiMO 2, wherein M is selected from one or more in transition metal Ni, Co and Mn, 0≤x≤1), circulate 100 times like this.After circulation finishes, treat that battery temperature recovers normal temperature, be full of electricity with 1C, then be discharged to 3.0V with 0.2C, draw residual capacity, residual capacity is obtained to capability retention divided by circulation volume first, acquired results is as shown in table 2.
Table 2. embodiment mono-~ eight and comparative example one ~ bis-lithium rechargeable battery cycle performance test
Battery Capacity surplus ratio (%)
Embodiment mono- A 91
Embodiment bis- B 91
Embodiment tri- C 92
Embodiment tetra- D 95
Embodiment five E 93
Embodiment six F 89
Embodiment seven G 91
Embodiment eight H 91
Comparative example one I 56
Comparative example two J 43
As can be seen from Table 2, adopt the lithium rechargeable battery that the embodiment of the present invention one to eight provides to be up to 95% at capability retention after 100 circulations, minimum is 89%, lithium rechargeable battery prepared in comparative example one and two only has 56% and 43% at capability retention after 100 circulations, this shows that the non-water organic electrolyte that the embodiment of the present invention one to eight provides has good high voltage bearing performance, the lithium rechargeable battery cycle performance that simultaneously adopts the embodiment of the present invention one to eight to provide is improved.

Claims (10)

1. a non-water organic electrolyte, is characterized in that, comprising:
Lithium salts;
Non-aqueous organic solvent; And
Non-water organic electrolysis solution additive, described non-water organic electrolysis solution additive is suc as formula the non-water organic electrolysis solution additive shown in (I) and/or suc as formula the non-water organic electrolysis solution additive shown in (II),
formula (I),
formula (II),
Wherein, R 1, R 2, R 3, R 4, R 5, R 6, R 7and R 8for C 1~ C 10straight or branched alkyl, C 1~ C 10alkylene, C 1~ C 10alkynes base or C 6~ C 14aromatic radical, or R 1, R 2, R 3, R 4, R 5, R 6, R 7and R 8for containing halogen: C 1~ C 10straight or branched alkyl, C 1~ C 10alkylene, C 1~ C 10alkynes base or C 6~ C 14aromatic radical.
2. the non-water organic electrolyte of one as claimed in claim 1, is characterized in that, described suc as formula R in the non-water organic electrolysis solution additive shown in (I) 1, R 2, R 3and R 4for methyl, ethyl, trifluoromethyl, trifluoroethyl, perfluor ethyl, phenyl, benzyl, part or perfluor substituted-phenyl.
3. the non-water organic electrolyte of one as claimed in claim 1, is characterized in that, described suc as formula R in the non-water organic electrolysis solution additive shown in (II) 5, R 6, R 7and R 8for methyl, ethyl, trifluoromethyl, trifluoroethyl, perfluor ethyl, phenyl, benzyl, part or perfluor substituted-phenyl.
4. the non-water organic electrolyte of one as claimed in claim 1, is characterized in that, by mass fraction, described non-aqueous organic solvent accounts for 85% ~ 99.5% of non-water organic electrolyte, and described non-water organic electrolysis solution additive accounts for 0.5% ~ 15% of non-water organic electrolyte.
5. the non-water organic electrolyte of one as claimed in claim 1, it is characterized in that, described non-water organic electrolyte also comprises function additive, and described function additive is selected from one or more in circulation additive, high temperature additive, flame-retardant additive and overcharging additive.
6. a preparation method for non-water organic electrolyte, is characterized in that, comprises the following steps:
Lithium salts is dissolved in non-aqueous organic solvent, adds suc as formula the non-water organic electrolysis solution additive shown in (I) and/or suc as formula the non-water organic electrolysis solution additive shown in (II), stir, make non-water organic electrolyte,
formula (I),
formula (II),
Wherein, R 1, R 2, R 3, R 4, R 5, R 6, R 7and R 8for C 1~ C 10straight or branched alkyl, C 1~ C 10alkylene, C 1~ C 10alkynes base or C 6~ C 14aromatic radical, or R 1, R 2, R 3, R 4, R 5, R 6, R 7and R 8for containing halogen: C 1~ C 10straight or branched alkyl, C 1~ C 10alkylene, C 1~ C 10alkynes base or C 6~ C 14aromatic radical.
7. the preparation method of a kind of non-water organic electrolyte as claimed in claim 6, is characterized in that, described suc as formula R in the non-water organic electrolysis solution additive shown in (I) 1, R 2, R 3and R 4for methyl, ethyl, trifluoromethyl, trifluoroethyl, perfluor ethyl, phenyl, benzyl, part or perfluor substituted-phenyl.
8. the preparation method of a kind of non-water organic electrolyte as claimed in claim 6, is characterized in that, described suc as formula R in the non-water organic electrolysis solution additive shown in (II) 5, R 6, R 7and R 8for methyl, ethyl, trifluoromethyl, trifluoroethyl, perfluor ethyl, phenyl, benzyl, part or perfluor substituted-phenyl.
9. the preparation method of a kind of non-water organic electrolyte as claimed in claim 6, it is characterized in that, by mass fraction, described non-aqueous organic solvent accounts for 85% ~ 99.5% of non-water organic electrolyte, and described non-water organic electrolysis solution additive accounts for 0.5% ~ 15% of non-water organic electrolyte.
10. a lithium rechargeable battery, it is characterized in that, comprise: positive pole, negative pole, barrier film, housing and non-water organic electrolyte, described non-water organic electrolyte, comprise: lithium salts, non-aqueous organic solvent and suc as formula the non-water organic electrolysis solution additive shown in (I) and/or suc as formula the non-water organic electrolysis solution additive shown in (II)
formula (I),
formula (II),
Wherein, R 1, R 2, R 3, R 4, R 5, R 6, R 7and R 8for C 1~ C 10straight or branched alkyl, C 1~ C 10alkylene, C 1~ C 10alkynes base or C 6~ C 14aromatic radical, or R 1, R 2, R 3, R 4, R 5, R 6, R 7and R 8for containing halogen: C 1~ C 10straight or branched alkyl, C 1~ C 10alkylene, C 1~ C 10alkynes base or C 6~ C 14aromatic radical.
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